Synthese und Kristallstruktur von Tetraphenylphosphonium-Aquabis(tetrasulfido)thionitrosyl-Osmat,PPh4[Os(NS)(S4)2(H2O)]

Synthesis and Crystal Structure of Tetraphenylphosphonium Aqua-bis(tetrasulfido)thionitrosyl Osmate, PPh₄[Os(NS)(S₄)₂(H₂O)] PPh₄[Os(NS)(S₄)₂(H₂O)] has been prepared as redbrown crystals by reacting PPh₄[OsNCl₄] with a solution of excess disodium tetrasulfide in dimethylformamide/H₂O and characterized by IR spectroscopy and by a crystal structure determination. Space group P2₁/n, Z = 4, structure solution with 4162 independent reflections, R = 0.059 for reflections with I > 2σ(I). Lattice dimensions at ?40°C: a = 1138.9(5), b = 1301.4(4), c = 2092.7(7) pm, β = 104.74(3)º. Os? N, Os? O, and Os? S distances are 175.2(12), 219.8(12), and 237.5(4)?239.1(4) pm, respectively. The Os?N?S moiety is approximately linear, with an OsNS angle of 171.2(7)º.     

Synthese und Kristallstruktur von (PPh4)2Se6

Synthesis and Crystal Structure of (PPh₄)₂Se₆ (PPh₄)₂Se₆ has been prepared by the reaction of selenium with K₂Se₂ in dimethylformamide solution in the presence of K₃[Mn(CN)₆] and PPh₄Br, forming black crystal needles. According to the crystal structure determination the compound consists of PPh⁺₄ ions and chainlike hexaselenide ions. Space group P6 , Z = 2,4683 Observed unique reflections, R = 0.066. Lattice dimensions at ?90°C: a = 951.0, b = 1094.8, c = 2137.4 pm, α = 82.66°, β = 83.36°, γ = 89.96°.     

Synthese und Kristallstrukturen der Polyselenidokomplexe (PPh4)6[M(Se4)2]2[WSe4] · DMF mit M = Zink und Quecksilber

Syntheses and Crystal Structures of the Polyselenido Complexes (PPh₄)₆[M(Se₄)₂]₂[WSe₄] · DMF with M = Zinc and Mercury The title compounds have been prepared by the reactions of the acetates of zinc and mercury, respectively, with excess (PPh₄)₂ WSe₄ in boiling dimethylformamide, forming black-red single crystals. According to the X-ray structure determinations both compounds crystallize isotypically in the space group 12/a with four formula units per unit cell. (PPh₄)₆[Zn(Se₄)₂]₂[WSe₄] · DMF: a = 2888.1(6), b = 1740.3(2), c = 2893.9(4) pm, β = 90.47(1)°. 3230 observed unique reflections, R = 0.009. (PPh₄)₆[Hg(Se₄)₂]₂[WSe₄] · DMF: a = 2891.8(5), b = 1738.0(4), c = 2920.1(5) pm, β = 90.29(2)°. 2978 observed unique reflections, R = 0.115%. The compounds consist of PPh₄⁺ ions, spirocyclic octaseleno metallates [M(Se₄)₂]^2?, tetrahedral WSe₄²-ions, and disordered DMF Molecules.     

Die Kristallstrukturen der Polytelluride [Ca(DMF)6]Te4, [Sr(15-Krone-5)2]Te4 · H2O, {[BaCl(18-Krone-6)(DMF)2]2[BaCl(18-Krone-6)(DMF) (H2O)]2(Te4)2} und [Ph3PNPPh3]2Te5 · 2 DMF

Crystal Structures of the Polytellurides [Ca(DMF)₆]Te₄, [Sr(15-Crown-5)₂]Te₄ · H₂O, {[BaCl(18-Crown-6)(DMF)₂]₂[BaCl(18-Crown-6)(DMF) (H₂O)]₂(Te₄)₂}, and [Ph₃PNPPh₃]₂Te₅ · 2 DMF The title compounds were formed by alkalimetal polytelluride solutions in dimethylformamide (DMF) in the presence of the corresponding counter ions as well as in the presence of 15-crown-5 or 18-crown-6. Single crystals were obtained upon using additional diethylether. [Ca(DMF)₆]Te₄: Space group C2/c, Z = 4, 1024 observed unique reflections, R = 0.055. Lattice dimensions at ?70°C: a = 1776.1; b = 813.0 c = 2545.9pm; β = 102.90°. The compound consists of centrosymmetric [Ca(DMF)⁶]²⁺ ions, in which the calcium ions are octahedrally coordinated by the six oxygen atoms of the DMF molecules, and chain-like Te [Sr)15-crown-5)₂]Te₄ · H₂O: Space group C2/c, Z = 4, 3322 observed unique reflections, R = 0.058. Lattice dimensions at ?70°C: a = 1450.5; b = 1407.3; c = 1660.9 pm; β = 110.22°. The compounds forms centrosymmetric cations [Sr(15-crown-5) ₂]²⁺, in which the Sr²⁺ ion is sandwich-like surrounded by the ten oxygen atoms of the crown ether molecules, and chain-like Te₄^2? ions, which are associated in the lattice forming polymeric chains. {[BaCl(18-crown-6)(DMF) ₂]₂[BaCl(18-crown-6)(DMF)· (H₂O)] ₂(Te₄)₂}: Space group P1 , Z = 1, 3189 observed unique reflections, R = 0.054. Lattice dimensions at 19°C: a = 986.1; b = 1052.8; c = 2696.4 pm; α = 89.34°; β = 88.68°; γ = 89.56°. The compound consists of chain-like Te ions without symmetry and of the two somewhat different cations [BaCl(18-crown-6)(DMF) ₂]₂²⁺, in which the Ba²⁺ ions dimerize via centroysmmetric rings. Along with the six oxygen atoms of the crown ether molecules and the oxygen atoms of the DMF molecules, the oxygen atoms of the DMF and water molecule, respectively, the Ba⁺ ions achieve coordination number ten. [Ph₃PNPPh₃]₂Te₅ · 2DMF: Space group Pc, Z = 2, 5971 observed unique reflections, R = 0.058. Lattice dimensions at 20°C: a = 20°C: a = 1085.2; b = 1287.0; c = 2715.9 pm; β = 90.19°. The compounds consists of [Ph₃PNPPh₃]₊ ions, chain-like Te₅^2? ions, and incorporate DME molecules without bonding interaction. The ₅^2? ions are associate via polymeric chains in which left- and right handed individuals are alternating.     

Die Kristallstrukturen von (NH4)2[ReCl6], [ReCl2(CH3CN)4]2[ReCl6] · 2CH3CN und [ReCl4(18-Krone-6)]

The Crystal Structures of (NH₄)₂[ReCl₆], [ReCl₂(CH₃CN)₄]₂[ReCl₆] · 2CH₃CN and [ReCl₄(18)(Crown-6)] Brown single crystals of (NH₄)₂[ReCl₆] are formed by the reaction of NH₄Cl with ReCl₅ in a suspension of diethylether. [ReCl₂(CH₃CN)₄]₂[ReCl₆] · 2CH₃CN crystallizes as brown crystal plates from a solution of ReCl₅ in acetonitrile. Lustrous green single crystals of [ReCl₄(18-crown-6)] are obtained by the reaction of 18-crown-6 with ReCl₅ in a dichloromethane suspension. All rhenium compounds are characterized by IR spectroscopy and by crystal structure determinations. (NH₄)₂[ReCl₆]: Space group Fm3 m, Z = 4, 75 observed unique reflections, R = 0.01. Lattice constant at ?70°C: a = 989.0(1) pm. The compound crystallizes in the (NH₄)₂[PtCl₆] type, the Re? Cl distance is 235.5(1) pm. [ReCl₂(CH₃CN)₄]₂[ReCl₆] · 2CH₃CN: Space group P1, Z = 1, 2459 observed unique reflections, R = 0.12. Lattice dimensions at ?60°C: a = 859.0(1), b = 974.2(7), c = 1287.3(7) pm, α = 102.69(5)°, b? = 105.24(7)°, γ = 102.25(8)°. The structure consists of two symmetry-independent [ReCl₂(CH₃CN)₄]⁺ ions with trans chlorine atoms, [ReCl₆]^2? ions, and included acetonitrile molecules. In the cations the Re? Cl bond lengths are 233 pm in average, in the anion they are 235 pm in average. [ReCl₄(18-crown-6)]: Space group P2₁/n, Z = 4, 3 633 observed unique reflections, R = 0.06. Lattice dimensions at ?70°C: a = 1040.2(4), b = 1794.7(5), c = 1090.0(5) pm, b? = 108.91(4)°. The compound forms a molecular structure, in which the rhenium atom is octahedrally coordinated by the four chlorine atoms and by two oxygen atoms of the crown ether molecule.     

Die Kristallstrukturen der Polyselenide [Cs(18-Krone-6)]2Se5 · DMF, [Rb(222-Crypt)]2Se6, [Ba(15-Krone-5)2]Se6 · DMF und [Na(12-Krone-4)2]2Se7

Crystal Structures of the Polyselenides [Cs(18-Crown-6)]₂Se₅ · DMF, [Rb(222-Crypt)]₂Se₆, [Ba(15-Crown-5)₂]Se₆ · DMF, and [Na(12-Crown-4)₂]Se₇ . The title compounds have been prepared by reactions of the corresponding diselenides with excess selenium in the presence of crown ethers in dimethylformamide solutions, forming black crystals. [Cs(18-Crown-6)]₂Se₅ · DMF: Space group P2₁/m, Z = 2, 2 194 observed unique reflections, R = 0.119. Lattice dimensions at 20°C: a = 1 041.2; b = 1 496.3; c = 1 459.7 pm; β = 100.39°. The compound forms an ionic triple with Cs…Se-contacts between 374 and 381 pm. [Rb(222-Crypt)]₂Se₆: Space group P1 , Z = 2, 7 405 observed unique reflections, R = 0.056. Lattice dimensions at – 70°C: a = 1 106.8; b = 1 460.8; c = 1 718.8 pm; α = 89.22°; β = 86.65°; γ = 71.53°. The compound contains Se₆^2? chains without direct contact with each other. [Ba(15-Crown-5)₂]Se₆ · DMF: Space group P2₁/n, Z = 4, 2 680 observed unique reflections, R = 0.055. Lattice dimensions at – 80°C: a = 1 051.9; b = 1 322.4; c = 2 729.9 pm; β = 100.93°. The compound contains Se₆^2? chains, which are isolated from each other by the cations and the included DMF molecules. [Na(12-Crown-4)₂]₂Se₇: Space group P1 , Z = 2, 7 313 observed unique reflections, R = 0.042. Lattice dimensions at – 70°C: a = 1 260.9; b = 1 433.6; c = 1 462.9 pm; α = 80.27°; β = 78.60°; γ = 69.34°. The compound contains Se₇^2? chains without direct contacts with each other.     

Synthese und Kristallstruktur von [Na(15-Krone-5)]4[Cd4Te12] · 8 DMF

Synthesis and Crystal Structure of [Na(15-Crown-5)]₄[Cd₄Te₁₂] · 8 DMF The title compound has been prepared by reaction of Na₂Te₃ with cadmium acetate in DMF solution in the presence of 15-crown-5, forming black crystal needles, which were characterized by an X-ray structure determination. Space group P2₁/n, Z = 2, 5 716 observed unique reflections, R = 0.038. Lattice dimensions at ?50°C: a = 1 622.9, b = 2 038.2, c = 1 739.8 pm, β = 92.26°. The compound has an ionic structure. The cations [Na(15-crown-5)(DMF)]⁺ and [Na(15-crown-5) · (DMF)₂]⁺ together with two further DMF molecules form tetrameric units. In the centrosymmetric anions [Cd₄Te₁₂]^4? the cadmium atoms are linked by μ₂-Te^2?-, μ₄-Te₂^2?-, and μ₂-Te₃^2?-units.     

Die Kristallstrukturen von SeCl3 +SbCl6−, SeBr3+GaBr4−, PCl4+SeCl5− und (PPh4+)2SeCl42− · 2 CH3CN

Crystal Structures of SeCl₃⁺SbCl₆^?, SeBr₃⁺GaBr₄^?, PCl₄⁺SeCl₅^?, and (PPh₄⁺)₂SeCl₄^2? · 2 CH₃CN The crystal structures of the title compounds were determined by X-ray diffraction. SeCl₃⁺SbCl₆^?: Space group P2₁/m, Z = 4, structure determination with 1795 observed unique reflections, R = 0.022. Lattice dimensions at ?80°C: a = 940.9, b = 1066.3, c = 1234.9 pm, β = 102.79°. The compound forms ion pairs with the structure of a double octahedron with linked surfaces. SeBr₃⁺GaBr₄^?: Space group Pc, Z = 2, structure determination with 1461 observed unique reflections, R = 0.058. Lattice dimensions at ?60°C: a = 660.1, b = 655.3, c = 1431.3 pm, β = 101.177°. The compound crystallizes in the SCl₃[AlCl₄] lattice type. Between the ions there are two relatively short Se … Br? Ga contacts. PCl₄⁺SeCl₅^?: Space group Ima2, Z = 8, structure determination with 1757 observed unique reflections, R = 0.029. Lattice dimensions at ?50°C: a = 1651.6, b = 1201.2, c = 1166.4 pm. The SeCl₅^? ions are associated to chains via interionic Se? Cl … Se contacts along the crystallographic c-axis. (PPh₄⁺)₂SeCl₄^2? · 2CH₃CN: Space group P2₁/n, Z = 2, structure determination with 2578 observed unique reflections, R = 0.050. Lattice dimensions at ?80°C: a = 1288.5, b = 726.0, c = 2585.8 pm, β = 101.65°. The compound includes planar-tetragonal SeCl₄^2? ions, which almost meet D_4h symmetry.     

Synthese und Kristallstrukturen der Phosphaniminato-Komplexe [SbF2(NPEt3)]2 und [SbF(NPEt3)2]2 sowie von NMe4+SbF4−

Synthesis and Crystal Structures of the Phosphoraneiminato Complexes [SbF₂(NPEt₃)]₂ and [SbF(NPEt₃)₂]₂ as well as of NMe₄⁺SbF₄^? The title compounds have been prepared from antimony trifluoride with the silylated phosphaneimine Me₃SiNPEt₃ and [NMe₄]F, respectively. They were characterized by IR spectroscopy and by crystal structure determinations. [SbF₂(NPEt₃)]₂ : Space group Pbca, Z = 8, structure determination with 1264 unique reflections, R₁ = 0.028 for reflections with I > 2σ(I). Lattice dimensions at ?80°C: a = 1284.8, b = 1162.4, c = 1380.4 pm. The compound forms centrosymmetric dimeric molecules, in which the Ψ-trigonal-bipyramidal coordinated antimony atoms are linked via μ₂-N bridges of the NPEt₃^? ligands. [SbF(NPEt₃)₂]₂ : Space group P2₁/c, Z = 4, structure determination with 2270 unique reflections, R₁ = 0.029 for reflections with I > 2μ(I). Lattice dimensions at ?75°C: a = 815.8, b = 1121.2, c = 2068.5 pm, β = 101.09°. The compound forms centrosymmetric dimeric molecules, in which the Ψ-trigonal-bipyramidal coordinated antimony atoms are linked via μ₂-N bridges of one of the two NPEt₃^? ligands. The other NPEt₃^? group is terminally connected. NMe₄⁺SbF₄^? : Space group P2₁/c, Z = 4, structure determination with 1503 unique reflections, R₁ = 0.069 for reflections with I > 2μ(I). Lattice dimensions at ?50°C: a = 539.80, b = 896.10, c = 1760.3 pm, β = 90.338°. The compound includes monomeric SbF₄^? ions with distorted Ψ-trigonal-bipyramidal environment of the antimony atoms.     

Synthese und Kristallstruktur von [Na(12-Krone-4)2]2[Hg(Se4)2] · 1,5 DMF

Synthesis and Crystal Structure of [Na(12-Crown-4)₂]₂[Hg(Se₄)₂] · 1.5 DMF . The title compound has been prepared by the reaction of Na₂Se₄ with mercury acetate in DMF solution in the presence of 15-crown-5, forming dark red crystal needles. [Na(12-crown-4)₂]₂[Hg(Se₄)₂] · 1.5 DMF crystallizes in the space group C2/c with eight formula units per unit cell. The structure was determined with 3 824 observed unique reflections, R = 0.085. Lattice dimensions at - 70°C: a = 2 884(2), b = 1 407.7(7), c = 2 843(2) pm, β = 93.93(5)°. The structure consists of [Na(12-crown-4)₂]⁺ ions with a sandwichlike coordination of the crown ether molecules, and of [Hg(Se₄)₂]^2? ions, in which the mercury atom is coordinated by two tetraselenido ions in a chelating fashion. The [Hg(Se₄)₂]^2? ions are arranged to infinite chains via Se…?Se contacts.     

Synthese und Kristallstruktur von (PPh4)2[Mo2NCl9]2, einem μ-Nitridokomplex mit Molybdän(V), und -(VI)

Synthesis and Crystal Structure of (PPh₄)₂[Mo₂NCl₉]₂, a μ-Nitrido Complex with Molybdenum (V) and (VI) The title compound is formed as a by-product in the partial oxidation of Mo₂NCl₇ with chlorine in POCl₃ solution, when the reaction mixture is treated with PPh₄Cl. The crystals, which are sensitive to moisture, are black in reflectance and red in transmittance. A more effective synthesis is the direct reaction of PPh₄[MoNCl₄] with MoCl₅ in dichloro methane. (PPh₄)₂[Mo₂NCl₉]₂ was characterized by the i.r. spectrum and by a structural analysis with X-ray data. The compound crystallizes triclinic in the space group P1 with two formula units per unit cell (9225 independent observed reflexions, R = 0.058). The cell parameters are (20°C): a = 1144 pm, b = 1517 pm, c = 2000 pm, α = 79.8°, β = 80.1°, γ = 72.1°. (PPh₄)₂[Mo₂NCl₉]₂ consists of PPh₄⊕ cations and the anions [Mo₂NCl₉]₂^22?, which dimerize via chloro bridges with Mo? Cl bons lengths of 243 pm and 287 pm. In the [Mo₂NCl₉]₂^2? units the molybdenum atoms are linked by Mo^VI?N? Mo^V bridges (bond angles 179° and 174°, resp.) with Mo? N bond lengths of 167 pm and 212 pm.     

Die Kristallstrukturen von [ReCl4(PhCCPh)]2 · 2 CH2Cl2 und von PPh4[ReOCl4]

Crystal Structures of [ReCl₄(PhC?CPh)]₂ · 2 CH₂Cl₂ and PPh₄[ReOCl₄] Single crystals of [ReCl₄(PhC?CPh)]₂ · 2 CH₂Cl₂ were obtained by chilling dilute solutions of the solvate [ReCl₄(PhC?CPh)POCl₃] in CH₂Cl₂. PPh₄[ReOCl₄] was formed by the reaction of the diphenyl acetylene complex [ReCl₅(PhC?CPh)] with PPh₄Cl · H₂O in CH₂Cl₂ solution. [ReCl₄(PhC?CPh)]₂ · 2 CH₂Cl₂: space group P2₁/c, Z = 2, 2244 observed independent reflexions, R = 0.038. Lattice parameters (19°C): a = 987.2 pm; b = 1533.9 pm; c = 1193.8 pm; β = 90.17° The compound forms centrosymmetrical dimeric molecules with ReCl₂Re bridges with Re? Cl distances of 241.2 and 267.6 pm. The longer Re? Cl bond is situated in trans-position to the equatorial, side-on coordinated diphenyl acetylene ligand with mean Re? C distances of 200 pm. PPh₄[ReOCl₄]: space group P4/n, Z = 2, 1487 observed, independent reflexions, R = 0.047. Lattice parameters (19°C): a = b = 1272.0 pm; c = 771.3 pm. The compound crystallizes in the AsPh₄[RuNCl₄] type; it consists of [ReOCl₄]^? anions and PPh₄⁺ cations. The anions are tetragonal with C_4v symmetry and bond lengths Re? O = 165.4 pm and Re? Cl = 232.6 pm; the bond angle OReCl is 106.7°.     

Synthese und Kristallstrukturen der silylierten Tris-Phosphanimine R?C(CH2PPh2NSiMe3)3 mit R  H und CH3

Synthesis and Crystal Structures of the Silylated λ⁵-Phosphazenes R? C(CH₂PPh₂NSiMe₃)₃ with R = H and CH₃ The title compounds are obtained by Staudinger reaction from the corresponding tripodal phosphanes R? C(CH₂PPh₂)₃ and trimethylsilylazide. Both complexes are characterized by their IR and NMR spectra and by crystal structure analyses. H? C(CH₂PPh₂NSiMe₃)₃ ( 1 ): Space group P2₁/c, Z = 4, structure determination with 7833 independent reflections, R = 0.055. Lattice dimensions at ?50°C: a = 1399.5, b = 2311.4, c = 1678.9 pm, β = 112.92°. CH₃? C(CH₂PPh₂NSiMe₃)₃ ( 2 ): Space group P1 , Z = 2, structure determination with 9251 independent reflections, R = 0.057. Lattice dimensions at ?50°C: a = 1276.5, b = 1386.9, c = 1790.2 pm; α = 85.55°, β = 69.39°, γ = 62.99°. 1 and 2 form monomeric molecules which are distinguished by their conformation.     

Phosphanimin- und Phosphaniminato-Komplexe von Bor. Synthese und Kristallstrukturen von [BF3(Me3SiNPEt3)], [BCl2(NPPh3)]2, [BCl2(NPEt3)]2, [B2Cl3(NPEt3)2]+BCl4− und [B2Cl2(NPiPr3)3]+BCl4−

Phosphaneimine and Phosphoraneiminato Complexes of Boron. Synthesis and Crystal Structures of [BF₃(Me₃SiNPEt₃)], [BCl₂(NPPh₃)]₂, [BCl₂(NPEt₃)]₂, [B₂Cl₃(NPEt₃)₂]⁺BCl₄^?, and [B₂Cl₂(NPⁱPr₃)₃]⁺BCl₄^? The title compounds have been prepared from the corresponding silylated phosphaneimines and boron trifluoride etherate and boron trichloride, respectively. The compounds form white moisture sensitive crystals, which were characterized by ¹¹B-nmr-spectroscopy, IR-spectroscopy and by crystal structure determinations. [BF₃(Me₃SiNPEt₃)] : Space group P2₁/c, Z = 4, R = 0.032 for reflections with I > 2σ(I). Lattice dimensions at ?70°C: a = 1361.0, b = 819.56, c = 1422.5 pm, β = 109.86°. The donor acceptor complex forms monomeric molecules with a B? N bond length of 157.8 pm. [BCl₂(NPPh₃)]₂ · 2 CH₂Cl₂ : Space group P2₁/c, Z = 2, R = 0.049 for reflections with I > 2σ(I). Lattice dimensions at ?50°C: a = 1184.6, b = 2086.4, c = 843.0 pm, β = 96.86°. The compound forms centrosymmetric dimeric molecules in which the boron atoms are linked to B₂N₂ four-membered rings with B? N distances of 152.7 pm via μ₂-N bridges of the NPPh₃ groups. [BCl₂(NPEt₃)]₂ : Space group Pbca, Z = 4, R = 0.029 for reflections with I > 2σ(I). Lattice dimensions at ?90°C: a = 1269.5, b = 1138.7, c = 1470.3 pm. The compound has a molecular structure corresponding to the phenyl compound with B? N ring distances of 151.0 pm. [B₂Cl₃(NPEt₃)₂]⁺BCl₄^? : Space group Pbca, Z = 8, R = 0.034 for reflections with I > 2σ(I). Lattice dimensions at ?70°C: a = 1309.3, b = 1619.8, c = 2410.7 pm. Within the cations the boron atoms are linked to planar, asymmetrical B₂N₂ four-membered rings with B? N distances of 155.1 and 143.1 pm via the μ₂-N atoms of the NPEt₃ groups. [B₂Cl₂(NPⁱPr₃)₃]⁺BCl₄^? · CH₂Cl₂: Space group Pna2, Z = 4, R = 0.033 for reflections with I > 2σ(I). Lattice dimensions at ?70°C: a = 1976.5, b = 860.2, c = 2612.7 pm. Within the cations the boron atoms are linked to planar, asymmetrical B₂N₂ four-membered rings with B? N distances of 153.7 and 150.5 pm via the μ₂-N atoms of two of the NPⁱPr₃ groups. The third NPⁱPr₃ group is terminally connected to the sp²-hybridized boron atom with a B? N distance of 133.5 pm and with a B? N? P bond angle of 165.3°.     

Phosphaniminato-Komplexe des Schwefels. Synthese und Kristallstrukturen von [O3SS(NPPh3)2] · CH3CN, [SO(NPPh3)2] und [SCl(NPMe3)2]Cl

Phosphorane Iminato Complexes of Sulfur. Syntheses and Crystal Structures of [O₃SS(NPPh₃)₂] · CH₃CN, [SO(NPPh₃)₂], and [SCl(NPMe₃)₂]Cl The title compounds have been prepared by the reaction of Me₃SiNPPh₃ with SO₂ and SOCl₂, respectively, and by the reaction of Me₃SiNPMe₃ with S₂Cl₂. They form colourless, moisture sensitive crystals, which were characterized by IR spectroscopy and by crystal structure determinations. [O₃SS((NPPh₃)₂)] · CH₃CN : Space group Pca2₁, Z = 4, structure solution with 4016 observed unique reflections, R = 0.050. Lattice dimensions at ?60°C: a = 1865.1, b = 1168.4, c = 1569.0 pm. The compound has a zwitterionic structure with a S? S bond length of 218.2 pm and bond lengths S? N of 161.2 and P? N of 160.1 pm. [SO(NPPh₃)₂] : Space group P2₁/c, Z = 4, structure solution with 2854 observed unique reflections, R = 0.113. Lattice dimensions at ?50°C: a = 1173.1, b = 1585.6, c = 1619.2 pm, b? = 98.13°. The compound forms monomeric molecules, in which the positions of S and N atoms are disordered in two positions. The bond lengths are S? N 166 pm and P? N 163 pm in average. [SCl(NPMe₃)₂]Cl : Space group P1 , Z = 2, structure solution with 2416 observed unique reflections, R = 0.038. Lattice dimensions at 20°C: a = 613.2, b = 1030.3, c = 1111.4 pm, α = 88.48°, b? = 88.01°, γ = 83.10°. The compound forms ions [SCl(NPMe₃)₂]⁺ and Cl^?. In the cation the sulfur atom is ?-tetrahedrally coordinated with a long S? Cl distance of 246.9 pm and bond lengths S? N of 155.3 pm and P? N of 164.3 pm in average.     

Thiochlorowolframate von Wolfram(V) und -(VI). Die Kristallstrukturen von PPh4[WSCl4] und (PPh4)2[WS2Cl4] · 2 CH2Cl2

Thiochlorowolframates with Tungsten(V) and (VI). Crystal Structures of PPh₄[WSCl₄] and (PPh₄)₂[WS₂Cl₄] · 2 CH₂Cl₂ Diamagnetic (NEt₄)₂[WSCl₄]₂, having tungsten atoms linked via sulfur atoms, is obtained by the reaction of WCl₅ with NEt₄SH as well as by the reduction of WSCl₄ with NEt₄I in dichloromethane. If the reduction is performed with PPh₄I, PPh₄[WSCl₄] with monomer anions is formed. Reaction of WCl₆ with H₂S in dichloromethane yields brown, insoluble WS₂Cl₂ which has terminal W?S groups and bridging W? S? W groups according to its IR spectrum. WS₂Cl₂ and PPh₄Cl react to afford PPh₄[WS₂Cl₃] · 2 CH₂Cl₂ and (PPh₄)₂[WS₂Cl₄] · 2 CH₂Cl₂. IR spectra are reported. The crystal structures of PPh₄[WSCl₄] and (PPh₄)₂[WS₂Cl₄] · 2 CH₂Cl₂ were determined by X-ray diffraction. PPh₄[WSCl₄]: tetragonal, space group P4/n, Z = 2, a = 1292.3 pm, c = 763.2 pm; R = 0.054 for 898 observed reflexions. The [WSCl₄]^? ion has the structure of a square pyramid with a rather short W?S bond of 206 pm length. (PPh₄)₂[WS₂Cl₄] · 2 CH₂Cl₂: triclinic, space group P1 , a = 1017.7, b = 1114.5, c = 1243.4 pm, α = 70.61, β = 79.73, γ = 80.80°; R = 0.076 for 1804 reflexions. The [WS₂Cl₄]^2? has cis configuration; as it is situated on an inversion center it shows positional disorder.     

Darstellung und Kristallstrukturen von neutralen und kationischen Kupfer(I)-Gemischtligandkomplexen mit Derivaten des Biimidazols und Triphenylphosphan

Preparation and Crystal Structures of Neutral and Cationic Copper(I) Mixed Ligand Complexes with Triphenylphosphane and Derivatives of Biimidazole Eight triphenylphosphanecopper(I) complexes with bibenzimidazole, tetramethylbiimidazole or tetrahydrobiimidazole were prepared and characterized so far as possible by elemental analysis, IR, ¹H-NMR and ³¹P-NMR spectra. The crystal structures of two complexes with bibenzimidazole were determined. [Cu(bbimH₂)(PPh₃)₂]Cl · CH₂Cl₂: Reaction of CuCl with bibenzimidazole in fused triphenylphosphane or [CuCl(PPh₃)₃] with bibenzimidazole in CH₂Cl₂. Space group P 1, Z = 2, 6440 observed independent reflections, R = 0.064 for refletions with I > 2σ(I). Lattice parameters at 203 K: a = 983.6; b = 1348.9; c = 1805.5 pm; α = 77.24; β = 80.90; γ = 85.81°. The crystal structure is built up by monomeric molecules with distorted tetrahedral coordination of the copper atom (CuN₂P₂) and bibenzimidazole as bidentate ligand. The chloride ion is linked by H-bonds with the NH groups of the bibenzimidazole. [{Cu(PPh₃)₂}₂(μ-bbim)] · 2 CH₂Cl₂: Reaction of [CuCl(PPh₃)₃] with the dipotassium salt of bibenzimidazole in CH₃OH/CH₂Cl₂. Space group P 1, Z = 1, 7192 observed independent reflections, R = 0.057 for reflections with I > 2σ(I). Lattice parameters at 203 K: a = 1334.1; b = 1386.8; c = 1443.7 pm; α = 107.51; β = 103.35; γ = 113.74°. The crystal structure is built up by centrosymmetric molecules with distorted tetrahedral coordination of the copper atoms (CuN₂P₂) and bibenzimidazolate(2–) as tetradentate bridging ligand.     

Synthese und Kristallstrukturen der Nitridodiolato-Osmate(VI) PPh4[OsNCl2(O2C2H4)] und PPh4[OsNCl2(O2C2Me4)] · 2 THF

Syntheses and Crystal Structures of the Nitridodiolato Osmates(VI) PPh₄[OsNCl₂(O₂C₂H₄)] and PPh₄[OsNCl₂(O₂C₂Me₄)] · 2 THF The title compounds were prepared by the reaction of PPh₄[OsNCl₄] with glycole and pinacole, respectively, in CH₂Cl₂ and THF, respectively, in the presence of triethylamine, forming orange-red single crystals. According to the crystal structure determinations the compounds have ionic structures. In the anions the nitrido ligand occupies the apical position of the distorted tetragonal pyramid, and the two chlorine atoms and the two oxygen atoms of the diolato ligands are in equatorial positions. PPh₄[OsNCl₂(O₂C₂H₄)] : Space group P2₁/n, Z = 4, 3 331 observed unique reflections, R = 0.031. Lattice dimensions at 19°C: a = 1 750.3, b = 816.8, c = 1 816.5 pm, β = 95.16°. PPh₄[OsNCl₂(O₂C₂Me₄)] · 2 THF : Space group P1 , Z = 2, 5 238 observed unique reflections, R = 0.051. Lattice dimensions at -80°C: a = 898.9, b = 1 405.1, c = 1 518.6 pm, α = 93.66°, β = 92.89°, γ = 92.51°.     

[Na(12-Krone-4)2]2[Ni(Se4)2] · DMF; Synthese,Kristallstruktur und magnetisches Verhalten

[Na(12-Crown-4)₂]₂[Ni(Se₄)₂] · DMF; Synthesis, Crystal Structure, and Magnetic Behaviour The title compound has been prepared from NiCl₂ and sodium polyselenide in dimethylformamide solution in the presence of 12-crown-4, forming black crystal needles. They were characterized by an X-ray structure determination, by FIR spectroscopy as well as by the magnetic behaviour. [Na(12-crown-4)₂]₂[Ni(Se₄)₂] · DMF crystallizes monoclinically in the space group P2₁, 3650 observed unique reflections, R = 0.046. Lattice dimensions at ?80°C: a = 1020.3(2); b = 1889.5(2); c = 1498.7(3) pm; β = 108.29(1)°. The compound has an ionic structure, in which the sodium atoms of the [Na(12-crown-4)₂]⁺ cations are coordinated by the oxygen atoms of the crown ether molecules in an antiprismatic fashion. The nickel atom of the anion [Ni(Se₄)₂]^2? is surrounded by four selenium atoms of the tetraselenide chelates in an almost planar environment. The DMF molecules are inserted in the lattice without a bonding interaction. The magnetic susceptibility observed in the temperature interval 4.2 to 330K can be interpreted by means of a ³E ground term and D₂ as local symmetry, which was established by X-ray crystallography.     

Phosphaniminato-Komplexe des Schwefels. Synthese und Kristallstrukturen von [SO(Cl)(NPPh3)], [SO2(Cl)(NPPh3)] und [SCl(NPPh3)2]Cl

Phosphorane Iminato Complexes of Sulfur. Synthesis and Crystal Structures of [SO(Cl)(NPPh₃)], [SO₂(Cl)(NPPh₃)], and [SCl(NPPh₃)₂]Cl The title compounds have been prepared by the reaction of Me₃SiNPPh₃ with SOCl₂, SO₂Cl₂, and SCl₂, respectively. They form colourless, moisture sensitive crystals, which were characterized by IR spectroscopy and by crystal structure determinations. [SO(Cl)(NPPh₃)]: Space group P2₁/n, Z = 4, structure determination with 2 434 observed unique reflections, R = 0.047. Lattice dimensions at 19°C: a = 1 304.8, b = 996.5, c = 1 339.5 pm, β = 93.75°. The compound forms monomeric molecules with a remarkably long S? Cl bond of 234.2 pm and distances SN and PN of 154.6 and 161.6 pm, respectively, which agree with double bonds. [SO₂(Cl)(NPPh₃)]: Space group P2₁/n, Z = 4, structure solution with 2 872 observed, unique reflections, R = 0.047. Lattice dimensions at 20°C: a = 956.9, b = 1 909, c = 1 002.0 pm, β = 106.06°. The compound forms monomeric molecules with distances S? Cl of 207.1 pm, SN of 154.5 pm, and PN of 161.6 pm. [SCl(NPPh₃)₂]Cl: Space group P2₁/c, Z = 4, structure solution with 5 224 observed, unique reflections, R = 0.042. Lattice dimensions at 20°C: a = 1 108.6, b = 1 603.8, c = 1 840.5 pm, β = 99.98°. The compound forms ions [SCl(NPPh₃)₂]⁺ and Cl^?. In the cation the sulfur atom is φ-tetrahedrally coordinated with a long S? Cl distance of 248.5 pm and SN bond lengths of 154.5 and 156.0 pm.